Carbon/oxygen ratios, clay composition and gas-hydrate saturation of ODP Leg 164 sites

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

(Table 1) Snow and sea ice thickness, solar heat input and solar heat used for melting at seven ice mass-balance buoys in the Arctic in 2008

There has been a marked decline in the summer extent of Arctic sea ice over the past few decades. Data from autonomous ice mass-balance buoys can enhance our understanding of this decline. These buoys monitor changes in snow deposition and ablation, ice growth, and ice surface and bottom melt. Results from the summer of 2008 showed considerable large-scale spatial variability in the amount of surface and bottom melt. Small amounts of melting were observed north of Greenland, while melting in the southern Beaufort Sea was quite large. Comparison of net solar heat input to the ice and heat required for surface ablation showed only modest correlation. However, there was a strong correlation between solar heat input to the ocean and bottom melting. As the ice concentration in the Beaufort Sea region decreased, there was an increase in solar heat to the ocean and an increase in bottom melting.

Rock magnetic, element, and color data of three sediment cores along the Senegalese continental margin

We present a suite of new high-resolution records (0-135 ka) representing pulses of aeolian, fluvial, and biogenic sedimentation along the Senegalese continental margin. A multiproxy approach based on rock magnetic, element, and color data was applied on three cores enclosing the present-day northern limit of the ITCZ. A strong episodic aeolian contribution driven by stronger winds and dry conditions and characterized by high hematite and goethite input was revealed north of 13°N. These millennial-scale dust fluxes are synchronous with North Atlantic Heinrich stadials. Fluvial clay input driven by the West African monsoon predominates at 12°N and varies at Dansgaard-Oeschger time scales while marine productivity is strongly enhanced during the African humid periods and marine isotope stage 5. From latitudinal signal variations, we deduce that the last glacial ITCZ summer position was located between core positions at 12°26' and 13°40'N. Furthermore, this work also shows that submillennial periods of aridity over northwest Africa occurred more frequently and farther south than previously thought.

Benthic foraminifera in Tertiary sediments of DSDP Leg 90 holes

Eocene through Pliocene benthic foraminifers were examined from seven sites located at middle and lower bathyal depths on the Lord Howe Rise in the Tasman Sea, from another site at lower bathyal depths in the Coral Sea, and from a site in the intermediate-depth, hemipelagic province of the Chatham Rise, east of southern New Zealand. Age-related, depth-related, and bioprovincial faunal variations are documented in this chapter. One new species, Rectuvigerina tasmana, is named. The paleoecologic indications of several key groups, including the miliolids, uvigerinids, nuttallitids, and cibicidids, are combined with sedimentologic and stable isotopic tracers to interpret paleoceanographic changes in the Tasman Sea. Because the total stratigraphic ranges of many bathyal benthic foraminifers are not yet known, most endpoints in the Tasman Sea are considered ecologically controlled events. The disappearances of Uvigerina rippensis and Cibicidoidesparki and the first appearances of U. pigmaea, Sphaeroidina bulloides, and Rotaliatina sulcigera at the Eocene/Oligocene boundary can be considered evolutionary events, as also can the first appearance of Cibicides wuellerstorfi in Zone NN5. Species which are restricted to the lower bathyal zone except during discrete pulses, most of which are related to the development of glacial conditions, include Melonis pompilioides, M. sphaeroides, Pullenia quinqueloba, Nuttallides umbonifera, and U. hispido-costata. Middle bathyal indigenes include U. spinulosa, U. gemmaeformis, Ehrenbergina marwicki, R. sulcigera, and all rectuvigerinids except Rectuvigerina spinea. Although the miliolids first occurred at lower bathyal depths, they were more common in the middle bathyal zone. Although the Neogene hispido-costate uvigerinids first developed at lower bathyal depths and at higher middle latitude sites, in the later Neogene this group migrated to shallower depths and became predominant also in the middle bathyal zone. Despite the relatively similar sedimentologic settings at the six middle bathyal Tasman sites, there was extensive intrageneric and intraspecific geographic variation. Mililiolids, strongly ornamented brizalinids, bolivinitids, Bulimina aculeata, Osangularia culter, and strongly porous morphotypes were more common at higher latitudes. Osangularia bengalensis, striate brizalinids such as Brizalina subaenariensis, Gaudryina solida, osangularids in general, and finely porous morphotypes were more common in the subtropics. There was strong covariance between faunas at lower middle latitude, lower bathyal Site 591, and higher middle latitude, middle bathyal Site 593. The following oceanographic history of the Tasman Sea is proposed; using the stable isotopic record as evidence for glacials and examining the ecologic correlations between (1) miliolids and carbonate saturation, (2) nuttallitids and undersaturated, cooled, or "new" water masses, (3) uvigerinids with high organic carbon in the sediment and high rates of sediment accumulation, and (4) cibicidids and terrestrial organic carbon. The glacial located near the Eocene/Oligocene boundary is characterized by the penetration of cooler, more corrosive waters at intermediate depths in high southern latitudes. This may have caused overturn, upwelling pulses, in other Tasman areas. The development of Neogenelike conditions began in the late Oligocene (Zone NP24/NP25) with the evolution of several common Neogene species. A large number of Paleogene benthics disappeared gradually through the course of the early Miocene, which was not well preserved at any Tasman site. Corrosive conditions shallowed into the middle bathyal zone in several pulses during the early Miocene. The development of glacial conditions in the middle Miocene was accompanied by major changes throughout the Tasman Sea. Sediment accumulation rates increased and high-productivity faunas and corrosive conditions developed at all but the lowest-latitude Site 588. This increase in productivity and accumulation rate is attributed to the eutrophication of Antarctic water masses feeding Tasman current systems, as well as to invigorated circulation in general. It overlaps with the beginning of the Pacific High-productivity Episode (10-5 Ma). During the latest Miocene glacial episode, corrosive conditions developed at lower bathyal depths, while cooler water and lower nutrient levels shallowed to middle bathyal depths. Lower input of terrestrial organic carbon may be related to the lower nutrient levels of this time and to the termination of the Pacific High-productivity Episode. The moderate glacial episode during the mid-Pliocene (Zone NN15/NN16, ~3.2 Ma) corresponds to a decline in sediment accumulation rates and a reorganization of faunas unlike that of all other times. New genera proliferate and indices for cool, noncorrosive conditions and high organic carbon expand throughout the middle bathyal zone coeval with the sedimentation rate decreases. By the latest Pliocene (about 2.5 Ma), however, during another glacial episode, faunal patterns typical of this and later glacials develop throughout the Tasman Sea. Benthic foraminiferal patterns suggest increased input of terrestrial organic matter to Tasman Sea sediments during this episode and during later glacials.

Diversity of ocean acidification effects on marine N2 fixers

Considering the important role of N2 fixation for primary productivity and CO2 sequestration, it is crucial to assess the response of diazotrophs to ocean acidification. Previous studies on the genus Trichodesmium suggested a strong sensitivity towards ocean acidification. In view of the large functional diversity in N2 fixers, the objective of this study was to improve our knowledge of the CO2 responses of other diazotrophs. To this end, the single-celled Cyanothece sp. and two heterocystous species, Nodularia spumigena and the symbiotic Calothrix rhizosoleniae, were acclimated to two pCO2 levels (380 vs. 980 µatm). Growth rates, cellular composition (carbon, nitrogen and chlorophyll a) as well as carbon and N2 fixation rates (14C incorporation, acetylene reduction) were measured and compared to literature data on different N2 fixers. The three species investigated in this study responded differently to elevated pCO2, showing enhanced, decreased as well as unaltered growth and production rates. For instance, Cyanothece increased production rates with pCO2, which is in line with the general view that N2 fixers benefit from ocean acidification. Due to lowered growth and production of Nodularia, nitrogen input to the Baltic Sea might decrease in the future. In Calothrix, no significant changes in growth or production could be observed, even though N2 fixation was stimulated under elevated pCO2. Reviewing literature data confirmed a large variability in CO2 sensitivity across diazotrophs. The contrasting response patterns in our and previous studies were discussed with regard to the carbonate chemistry in the respective natural habitats, the mode of N2 fixation as well as differences in cellular energy limitation between the species. The group-specific CO2 sensitivities will impact differently on future biogeochemical cycles of open-ocean environments and systems like the Baltic Sea and should therefore be considered in models estimating climate feedback effects.

Hysteresis between coral reef calcification and the seawater aragonite saturation state

Some predictions of how ocean acidification (OA) will affect coral reefs assume a linear functional relationship between the ambient seawater aragonite saturation state (Omega a) and net ecosystem calcification (NEC). We quantified NEC in a healthy coral reef lagoon in the Great Barrier Reef during different times of the day. Our observations revealed a diel hysteresis pattern in the NEC versus Omega a relationship, with peak NEC rates occurring before the Omega a peak and relatively steady nighttime NEC in spite of variable Omega a. Net ecosystem production had stronger correlations with NEC than light, temperature, nutrients, pH, and Omega a. The observed hysteresis may represent an overlooked challenge for predicting the effects of OA on coral reefs. If widespread, the hysteresis could prevent the use of a linear extrapolation to determine critical Omega a threshold levels required to shift coral reefs from a net calcifying to a net dissolving state.

Effect of increased pCO2 on bacterial assemblage shifts in response to glucose addition in Fram Strait seawater mesocosms

Ocean acidification may stimulate primary production through increased availability of inorganic carbon in the photic zone, which may in turn change the biogenic flux of dissolved organic carbon (DOC) and the growth potential of heterotrophic bacteria. To investigate the effects of ocean acidification on marine bacterial assemblages, a two-by-three factorial mescosom experiment was conducted using surface sea water from the East Greenland Current in Fram Strait. Pyrosequencing of the V1-V2 region of bacterial 16S ribosomal RNA genes was used to investigate differences in the endpoint (Day 9) composition of bacterial assemblages in mineral nutrient-replete mesocosms amended with glucose (0 µm, 5.3 µm and 15.9 µm) under ambient (250 µatm) or acidified (400 µatm) partial pressures of CO2 (pCO2). All mesocosms showed low richness and diversity by Chao1 estimator and Shannon index, respectively, with general dominance by Gammaproteobacteria and Flavobacteria. Nonmetric multidimensional scaling analysis and two-way analysis of variance of the Jaccard dissimilarity matrix (97% similarity cut-off) demonstrated that the significant community shift between 0 µm and 15.9 µm glucose addition at 250 µatm pCO2 was eliminated at 400 µatm pCO2. These results suggest that the response potential of marine bacteria to DOC input may be altered under acidified conditions.

Predominance of heavily calcified coccolithophores at low CaCO3 saturation during winter in the Bay of Biscay

Coccolithophores are an important component of the Earth system, and, as calcifiers, their possible susceptibility to ocean acidification is of major concern. Laboratory studies at enhanced pCO2 levels have produced divergent results without overall consensus. However, it has been predicted from these studies that, although calcification may not be depressed in all species, acidification will produce "a transition in dominance from more to less heavily calcified coccolithophores" [Ridgwell A, et al., (2009) Biogeosciences 6:2611-2623]. A recent observational study [Beaufort L, et al., (2011) Nature 476:80-83] also suggested that coccolithophores are less calcified in more acidic conditions. We present the results of a large observational study of coccolithophore morphology in the Bay of Biscay. Samples were collected once a month for over a year, along a 1,000-km-long transect. Our data clearly show that there is a pronounced seasonality in the morphotypes of Emiliania huxleyi, the most abundant coccolithophore species. Whereas pH and CaCO3 saturation are lowest in winter, the E. huxleyi population shifts from <10% (summer) to >90% (winter) of the heavily calcified form. However, it is unlikely that the shifts in carbonate chemistry alone caused the morphotype shift. Our finding that the most heavily calcified morphotype dominates when conditions are most acidic is contrary to the earlier predictions and raises further questions about the fate of coccolithophores in a high-CO2 world.

Ba/Sr ratio in marine barite from five DSDP and ODP holes

The Paleocene-Eocene Thermal Maximum (PETM), ca. 55 Ma, was a period of extreme global warming caused by rapid emission of greenhouse gases. It is unknown what ended this episode of greenhouse warming, but high oceanic export productivity over thousands of years (as indicated by high accumulation rates of barium, Ba) may have been a factor in ending this warm period by carbon sequestration. However, Ba has a short oceanic residence time (~10 k.y.), so a prolonged global increase in Ba accumulation rates requires an increase in input of Ba to the ocean, increasing barite saturation. We use a novel proxy for barite saturation (Sr/Ba in marine barite) to demonstrate that the seawater saturation state with respect to barite did not change across the PETM. The observations of increased barite burial, no change in saturation, and the short residence time can be reconciled if Ba burial decreased at continental margin and shelf sites due to widespread occurrence of suboxic conditions, leading to Ba release into the water column, combined with increased biological export production at some pelagic sites, resulting in Ba sink reorganization.

Paleomagnetic of ODP Leg 133 holes

Paleomagnetic and rock-magnetic analyses from discrete samples of carbonate sites on the Queensland Plateau were used to determine magnetic polarity reversal stratigraphy and the nature of magnetization in these sediments. Magnetic polarity zones were correlated with the geomagnetic polarity time scale in the upper portions of cores at Sites 812 through 814, usually back to a late Pliocene age. Loss of reliable directional data was coincidental with a major decrease in magnetic intensity, below which, no stable polarity zones could be identified. The intensity reduction is either an in-situ alteration of magnetic grains, or an input signal representing progressive increase in the magnetic component of Queensland Plateau sediments. Although not conclusive at this point, the geochemical conditions and differing age of intensity reduction support the former hypothesis. Rock-magnetic analysis of carbonate sediments suggests that ultrafine-grained magnetite or maghemite crystals is an important carrier of remanence and may be biogenic in origin. Application of a recently calibrated anhysteretic remanent magnetization test to assess configuration of single-domain crystal within a natural matrix indicates that cementation (ooze-chalk-limestone) may be important in post-depositional changes affecting magnetostatic grain interaction.

CaCO3 size distribution in surface sediments

Lysocline reconstructions play an important role in scenarios purporting to explain the lowered atmospheric CO2 content of glacial time. These reconstructions are based on indicators such as the CaCO3 content, the percent of coarse fraction, the ratio of fragments to whole foraminifera shells, the ratio of solution-susceptible to solution-resistant species, and the ratio of coarse to fine CaCO3. All assume that changes with time in the composition of the input material do not bias the result. However, as the composition of the input material does depend on climate, none of these indicators provides an absolute measure of the extent of dissolution. In this paper we evaluate the reliability of the ratio of >63 µm CaCO3 to total CaCO3 as a dissolution indicator. We present here results that suggest that in today's tropics this ratio appears to be determined solely by CO3= ion concentration and water depth (i.e., the saturation state of bottom waters). This finding offers the possibility that the size fraction index can be used to reconstruct CO3= ion concentrations for the late Quaternary ocean to an accuracy of ±5 µmol/kg.

Oceanography and methane of waters from the Lena Delta

The Lena River is one of the largest Russian rivers draining into the Laptev Sea. The permafrost areas surrounding the Lena are predicted to thaw at increasing rates due to global temperature increases. With this thawing, large amounts of carbon - either organic or in the gaseous forms carbon dioxide and methane - will reach the waters of the Lena and the adjacent Buor-Khaya Bay (Laptev Sea). Methane concentrations and the isotopic signal of methane in the waters of the Lena Delta and estuary were monitored from 2008 to 2010. Creeks draining from permafrost soils produced hotspots for methane input into the river system (median concentration 1500 nM) compared with concentrations of 30-85 nM observed in the main channels of the Lena. No microbial methane oxidation could be detected; thus diffusion is the main process of methane removal. We estimated that the riverine diffusive methane flux is 3-10 times higher than the flux from surrounding terrestrial environment. To maintain the observed methane concentrations in the river, additional methane sources are necessary. The methane-rich creeks could be responsible for this input.